CN110506138B - Porous fiber and adsorption column - Google Patents

Porous fiber and adsorption column Download PDF

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Publication number
CN110506138B
CN110506138B CN201880022039.XA CN201880022039A CN110506138B CN 110506138 B CN110506138 B CN 110506138B CN 201880022039 A CN201880022039 A CN 201880022039A CN 110506138 B CN110506138 B CN 110506138B
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Prior art keywords
porous fiber
powder
fiber
less
porous
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CN201880022039.XA
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CN110506138A (en
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韩爱善
藤枝洋暁
上野良之
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Toray Industries Inc
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Toray Industries Inc
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    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/24—Formation of filaments, threads, or the like with a hollow structure; Spinnerette packs therefor
    • D01D5/247—Discontinuous hollow structure or microporous structure
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/52—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polymers of unsaturated carboxylic acids or unsaturated esters
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    • B01J20/285—Porous sorbents based on polymers
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    • A61M1/00—Suction or pumping devices for medical purposes; Devices for carrying-off, for treatment of, or for carrying-over, body-liquids; Drainage systems
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    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/10—Other agents for modifying properties
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/02—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F6/16—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polymers of unsaturated carboxylic acids or unsaturated organic esters, e.g. polyacrylic esters, polyvinyl acetate
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
    • D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
    • D01F8/10—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one other macromolecular compound obtained by reactions only involving carbon-to-carbon unsaturated bonds as constituent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/46—Materials comprising a mixture of inorganic and organic materials
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
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Abstract

The purpose of the present invention is to provide a porous fiber that achieves both suppression of exposure and separation of powder and granules and improvement in adsorption performance; an adsorption column filled with the porous fiber; a blood purification system is obtained by connecting an adsorption column and a dehydration column. In order to achieve the above object, the porous fiber of the present invention has the following constitution. That is, a porous fiber having a three-dimensional microporous structure formed by a solid-shaped fiber, and satisfying all of the following requirements: (1) a powder or granule having a diameter of 200 [ mu ] m or less, wherein the powder or granule having a diameter of 200 [ mu ] m or less has an area occupancy of 3.0% or more in a cross section of the three-dimensional microporous structure; (2) the powder or granule having a diameter of 200 μm or less is not contained in a region within 1.0 μm in the depth direction from the outermost surface.

Description

Porous fiber and adsorption column
Technical Field
The present invention relates to porous fibers. Furthermore, it relates to an adsorption column filled with porous fibers. Further, the present invention relates to a blood purification system in which an adsorption column and a water removal column are connected.
Background
Conventionally, powder and granular materials have been used as an adsorbent for adsorbing and removing a removal target substance in a treatment target liquid. Since the powder or granule itself is poor in handling properties alone, it is used by being carried on a fiber or the like. In this case, in order to improve the adsorption performance of the powder or granule on the removal target substance, it is necessary to shorten the distance between the liquid to be treated and the powder or granule as much as possible. However, if the liquid to be treated is in direct contact with the powder or granule, the powder or granule may be damaged by a flow stress generated when the liquid to be treated is passed therethrough, or the powder or granule may flow out from the fiber or the like on which the powder or granule is supported. Further, in the case of using blood as the liquid to be treated, if the particulate matter is in direct contact with the blood cell component, there is a possibility that undesired activation of blood may be caused. Therefore, it is important to design the position of the particulate matter in the fiber and the flow path of the particulate matter for efficiently guiding the removal target substance in the treatment target liquid into the fiber.
For example, patent document 1 discloses an invention relating to a fiber for clothing containing a powder or granule in a core portion and a sheath portion.
Similarly, patent document 2 specifies that the sheath portion also contains a powder or granule. Further, there is a description that the core portion is composed of only powder and granular material.
On the other hand, an invention in which the liquid to be treated does not come into direct contact with the powder or granule is also disclosed. Patent document 3 discloses an invention relating to a separation membrane containing a powder and granular material for water treatment.
Documents of the prior art
Patent document
Patent document 1: japanese laid-open patent publication No. 2014-189937
Patent document 2: japanese Kokai publication 2008-510083
Patent document 3: japanese patent laid-open No. 2010-227757.
Disclosure of Invention
Problems to be solved by the invention
However, as described in patent document 1, in the clothing fiber including the powder and granular material in the core portion and the sheath portion, there is no disclosure regarding the method for preventing the powder and granular material from being exposed on the fiber surface.
In a structure in which the sheath portion also includes the powder or granule and the core portion is composed of only the powder or granule as described in patent document 2, when the fiber is broken by external pressure, the powder or granule may be peeled off from the cross section of the filament. Similarly, there is no disclosure about the prevention of the exposure of the particulate matter on the fiber surface.
Further, in the case where the layer containing an adsorbent has a spherical structure as described in patent document 3, it may be difficult to control the flow path of the liquid to be treated, and variations in the flow path diameter may become large. In addition, particularly between the spherical structure and the spherical structure, the loading property of the powder or granule may be lowered.
As described above, conventionally proposed fibers containing a powder or granule focus on improving the addition rate of the powder or granule and imparting mechanical strength to the fiber for the purpose of improving performance, and no description is found on means for suppressing the powder or granule from being exposed on the fiber surface and peeling from the cross section.
Accordingly, the present invention provides a porous fiber that achieves both suppression of exposure and separation of powder and granular material and improvement of adsorption performance. Further, an adsorption column packed with the porous fiber is provided. Further, a blood purification system is provided in which the adsorption column and the dehydration column are connected.
Means for solving the problems
The present inventors have conducted extensive studies to solve the above problems, and as a result, have found that a porous fiber having excellent adsorption performance and high safety is obtained while suppressing exposure of powder and granular materials.
Further, the porous fiber of the present invention can adsorb and remove a polymer compound having an adsorption performance different from that of the encapsulated powder.
That is, the porous fiber of the present invention has the following configuration.
A porous fiber having a three-dimensional microporous structure formed by a solid-shaped fiber, and satisfying all of the following requirements:
(1) a powder or granule having a diameter of 200 [ mu ] m or less, wherein the powder or granule having a diameter of 200 [ mu ] m or less has an area occupancy of 3.0% or more in a cross section of the three-dimensional microporous structure;
(2) the powder or granule having a diameter of 200 μm or less is not contained in a region within 1.0 μm in the depth direction from the outermost surface.
ADVANTAGEOUS EFFECTS OF INVENTION
The present invention can provide a porous fiber that can suppress the exposure and separation of powder and granular material and improve the adsorption performance at the same time. Further, an adsorption column packed with the porous fiber can be obtained. Further, a blood purification system in which the adsorption column and the water removal column are connected to each other can be obtained.
Detailed Description
The porous fiber, the adsorption column and the blood purification system of the present invention are specifically described below.
The porous fiber of the present invention has a three-dimensional microporous structure formed by a solid-shaped fiber, and satisfies all of the following requirements:
(1) a powder or granule having a diameter of 200 μm or less, wherein the powder or granule having a diameter of 200 μm or less has an area occupancy of 3.0% or more in a cross section of the three-dimensional microporous structure;
(2) the powder or granule having a diameter of 200 μm or less is not contained in a region within 1.0 μm in the depth direction from the outermost surface.
The solid fibers referred to in the present invention are solid fibers having a fiber shape or form without a hollow portion.
In addition, in the present invention, the porous fiber has a three-dimensional microporous structure. The three-dimensional microporous structure refers to a structure having micropores which extend three-dimensionally and are partitioned.
In the present invention, the porous fiber has numerous fine pores continuously in the outside and inside thereof. Such a microporous structure forms a flow path for efficiently guiding a removal target substance in a treatment target liquid to the powder or granule in the fiber. Further, in the case where the substance to be removed is a polymer compound, such a microporous structure can be removed by adsorption while leaving the polymer compound in the micropores.
Therefore, in the present invention, the average pore radius of the three-dimensional pore structure is preferably in a specific range. That is, in the porous fiber of the present invention, the average pore radius of the three-dimensional pore structure is preferably in the range of 0.5nm or more and 100nm or less. The lower limit of the average pore radius of the three-dimensional pore structure is preferably 0.5nm, more preferably 1.5nm, and particularly preferably 2.0nm, while the upper limit thereof is preferably 100nm, more preferably 40nm, and particularly preferably 25 nm. If the average pore radius is small, the removal target substance cannot enter the pores, and thus the adsorption efficiency sometimes decreases. On the other hand, even if the pore radius is too large, the removal target substance may fall off without being fixed in the void part, and thus the adsorption efficiency may be conversely lowered. In the above pore size range, there is an optimum pore size depending on the size of the removal target substance. If the average pore radius is within the above range, the low-molecular compound is easily guided to the powder and granules in the fiber with good efficiency and adsorbed and removed, and the high-molecular compound is easily left in the pores of the porous fiber and adsorbed and removed.
In the porous fiber of the present invention, it is preferable that the micropores in the three-dimensional micropore structure selectively adsorb a polymer compound having a molecular weight of 1000 or more. The molecular weight of the selectively adsorbed polymer compound is more preferably 2000 or more, still more preferably 3000 or more, and still more preferably 5000 or more. On the other hand, while selective adsorption of a high molecular weight compound is possible by increasing the micropores, if the micropores are too large, the strength of the porous fiber is insufficient, and therefore, the upper limit is preferably 100 ten thousand, more preferably 80 ten thousand, further preferably 50 ten thousand, and further more preferably 20 ten thousand. Here, the selective adsorption of a high molecular weight compound having a molecular weight of 1000 or more means that the high molecular weight compound having a molecular weight of 1000 or more is adsorbed more than a low molecular weight compound having a molecular weight of less than 1000 in the blood concentration range of a dialysis patient. As a method for determining whether or not a polymer compound having a molecular weight of 1000 or more is selectively adsorbed, a porous fiber is sliced into a thickness of 1 μm in the fiber length direction with a microtome, and a sample containing no powder or granule and a sample containing powder or granule are prepared. 50mg of a sample containing no powder and 50mg of a sample containing powder were immersed in 50mL of bovine plasma and soaked at 37 ℃ for 4 hours, and then the adsorption performance (average adsorption mass of 1 g) of 1g on the average was determined from the difference in concentration between before and after immersion. When a high molecular weight compound having a molecular weight of 1000 or more is adsorbed more in a sample containing no powder than in a sample containing powder, the high molecular weight compound having a molecular weight of 1000 or more is selectively adsorbed. The method for determining the adsorption mass of 1g on average differs depending on the adsorption object, and for example, when the low-molecular compound having a molecular weight of 1000 or less is urea, uric acid, or creatinine, the adsorption mass of 1g on average can be determined by an enzymatic method. In the case of inorganic phosphorus, the adsorption mass of 1g on average can be determined by the direct molybdic acid method. On the other hand, in the case where the compound having a molecular weight of 1kDa or more is. beta.2MG, the adsorption amount can be determined by a latex immunoagglutination method. In the present specification, the molecular weight 1000 may be abbreviated as 1 kD. In order to selectively adsorb a polymer compound having a molecular weight of 1kDa or more, the average pore radius is preferably in the above range.
Here, the polymer compound as the removal target substance is not particularly limited.
The porous fiber of the present invention is preferably used for medical use. The porous fiber of the present invention is used for medical applications, for example, in medical devices described below. That is, the adsorption column is not particularly limited, and examples thereof include a dialysis membrane used in artificial dialysis, and an adsorption column used in applications where the adsorption column is directly in contact with blood and adsorbs harmful substances in blood. When used for medical purposes, there are mentioned substances which are present in blood and whose properties are themselves harmful, and substances which exhibit harmful effects due to their excessive presence. Examples of the polymer compound which is harmful or exhibits a harmful effect include cytokines, HMGB1, oncogenesis protein, and β 2 Microglobulin (. beta.2MG),. alpha.1microglobulin (. alpha.1MG), anti-A antibody, anti-B antibody, anti-acetylcholine receptor antibody, anti-cardiolipin antibody, anti-DNA antibody, immune complex, bile acid, hypnotic substance, drug, and rheumatic factor. On the other hand, albumin (molecular weight 66kDa) as a nutritional protein is preferably not adsorbed as much as possible. Specifically, examples of the substance to be removed include cytokines (molecular weight 8 to 30kDa), β 2MG (molecular weight 12kDa), HMGB1 (molecular weight 30kDa), and α 1MG (molecular weight 33 kDa). In particular, canTo cite the insufficient β 2MG removal indicated in extracorporeal circulation.
In the present invention, a cytokine is a protein that acts on the proliferation, differentiation, and functional expression of cells. Examples thereof include interleukin-1 beta, interleukin-2, interleukin-3, interleukin-4, interleukin-6, interleukin-8, TNF alpha, M-CSF, G-CSF, GM-CSF, interferon alpha, interferon beta, interferon gamma, TGF-beta, SCF, BMP, EGF, KGF, FGF, IGF, PDGF, HGF, and VEGF. The cytokine in the present invention refers to an inflammatory cytokine, and specifically includes interleukin-1 β, interleukin-6, interleukin-8 and TNF α.
If the average pore radius of the three-dimensional pore structure of the removal target substance is within the above range, the removal target substance can be adsorbed on the porous fiber of the present invention with good efficiency.
The average micropore radius of the porous fiber of the present invention is determined by Differential Scanning Calorimetry (DSC) measurement using a Differential Scanning Calorimeter (DSC). Specifically, the freezing point depression degree was measured by capillary aggregation of water in the micropores, and was determined as the 1 st-order average micropore radius. The adsorbent was quenched to-55 ℃ and heated to 5 ℃ at 0.3 ℃/min for measurement, the peak temperature of the obtained curve was taken as the melting point, and the 1-time average pore radius of the micropores was calculated from the following formula 1. For the measurement and calculation methods, reference is made to the description OF p104 in Kazuhiko Ishikiriyama et al; JOURNAL OF COLLOID AND INTERFACE SCIENCE, VOL.171,103-111 (1995)).
Formula 1
Average pore radius [ nm ] = (33.30-0.3181 x melting point depression [ deg.C ])/melting point depression [ deg.C ] 1 time
The porous fiber of the present invention can further improve the adsorption performance by increasing the specific surface area of the micropores in order to adsorb a substance to be removed. Therefore, in the porous fiber of the present invention, the specific surface area of the micropores in the aforementioned three-dimensional microporous structure is preferably 10m 2 More than g. The lower limit of the specific surface area of the micropores is preferably 10m 2 (ii) g, more preferably 20m 2 (iv)/g, more preferably 30m 2 (iv)/g, furtherPreferably 40m 2 Per g, particularly preferably 50m 2 (iv) g. On the other hand, if the specific surface area of the micropores is too large, the mechanical strength of the porous fiber is insufficient, and therefore, the upper limit of the specific surface area of the micropores is preferably 1000m 2 (iv)/g, more preferably 800m 2 (ii) g, more preferably 650m 2 G, even more preferably 500m 2 /g。
The specific surface area of the micropores was measured by DSC in the same manner as the method for measuring the average micropore radius. The method for calculating the specific surface area of micropores is described in p104 of the above-mentioned document.
The porous fiber of the present invention has a particulate body having a diameter of 200 μm or less. The diameter is preferably 200 μm or less, more preferably 100 μm or less, and particularly preferably 50 μm or less, because the particle size is preferably as small as possible. If the diameter is 200 μm or less, for example, when the powder or granule is used by being supported inside a porous fiber, the spinneret is less likely to be clogged at the time of spinning, and the spinning performance is less likely to be deteriorated, which is preferable. Further, the smaller the diameter, the larger the specific surface area, and the more easily the adsorption efficiency is improved. However, in the case where the diameter is smaller than the micropores of the porous fiber, the powder or granule may be eluted into the treatment target liquid such as blood through the micropores, and therefore, the diameter is preferably larger than the diameter of the micropores, and specifically, the diameter may be preferably larger than 100 nm. However, when the powder or granule is an aggregate of primary particles, the aggregate of primary particles may be in the above-mentioned diameter range, and the primary particle diameter does not need to be in the above-mentioned diameter range.
The diameter of the particulate supported on the porous fiber was observed by a scanning electron microscope (for example, S-5500 manufactured by Hitachi ハイテクノロジーズ Co., Ltd.). First, the porous fiber is sufficiently wetted and then immersed in liquid nitrogen, and the moisture in the micropores is instantaneously frozen by the liquid nitrogen. Thereafter, the porous fiber was rapidly bent, and the frozen water was removed in a vacuum dryer of 0.1torr or less in a state where the cross section of the porous fiber was exposed, to obtain a dried sample. Then, a thin film of platinum (Pt), platinum-palladium (Pt-Pd), or the like is formed on the surface of the porous fiber by sputtering to prepare an observation sample. Subjecting the sample to a reactionThe cross section of (A) was observed with a scanning electron microscope. An electron microscope image of a fiber cross section including a visual field of the powder/granular material was taken with a scanning electron microscope (1000 times), and diameters of arbitrary 30 powder/granular materials were measured and determined by number average. When the shape is a shape other than a circle, if the diameter of a circle inscribed in the shape is denoted by "a" and the diameter of a circle circumscribed by the shape is denoted by "b", then (a × b) 0.5 The equivalent circle diameter is obtained. In the case of aggregation of the powder or granule, the diameter of a circle inscribed in the aggregate is denoted by "a" and the diameter of a circle circumscribed by the aggregate is denoted by "b", and the equivalent circle diameter is determined in the same manner as described above.
The inscribed circle is a circle that is inscribed at least 2 points in the curve forming the cross-sectional profile of the fiber, is present only inside the fiber, and has the maximum diameter that can be obtained in a range where the circumference of the inscribed circle does not intersect the curve forming the cross-sectional profile of the fiber. In addition, the circumscribed circle means a circle having the largest diameter among arbitrary 2-point circles in the fiber cross-sectional profile.
In addition, when the porous fiber is broken by applying a physical force from the outside, it is important to reduce the risk that the powder and granular material is peeled off from the broken fiber section and flows out to the outside. Therefore, the particulate matter used in the present invention is preferably used by being supported inside the porous fiber. The state in which the powder or granule is supported inside is mainly a state in which the powder or granule is physically mixed with the porous fiber and adhered and held inside the porous fiber without impairing the function thereof. However, the state of being physically mixed with the porous fiber is not necessarily limited, and a case where the powder or granule is chemically bonded to the constituent molecules inside the porous fiber may be referred to as a state where the powder or granule is supported inside as long as the function of the powder or granule is not impaired.
In the present invention, the area occupancy rate of the particulate body supported inside the porous fiber in the cross section of the three-dimensional microporous structure is 3.0% or more. The lower limit of the area occupancy is preferably 5.0%, more preferably 10%, and still more preferably 20%. The upper limit of the area occupancy is preferably 80%, more preferably 70% or less, and still more preferably 60% or less. When the area occupancy of the powder/granular material is 3.0% or more, the amount of the porous fiber required to exhibit sufficient adsorption performance can be easily reduced when the column is produced, and the column volume can be easily reduced. On the other hand, the area occupancy rate of the particulate matter in the cross section of the porous fiber is preferably 80% or less in order to easily obtain sufficient fiber strength of the porous fiber and to easily improve spinnability. Further, since the powder and granular material are supported by the fiber material, when the fiber is broken by external pressure, the powder and granular material are easily prevented from being peeled off from the cross section of the filament.
The area occupancy of the particulate matter in the cross section of the porous fiber can be measured by the following method.
First, the porous fiber is sufficiently wetted and then immersed in liquid nitrogen, and the moisture in the micropores is instantaneously frozen by the liquid nitrogen. Thereafter, the porous fiber was rapidly bent, and the frozen water was removed in a vacuum dryer of 0.1torr or less in a state where the cross section of the porous fiber was exposed, to obtain a dried sample. Then, a thin film of platinum (Pt), platinum-palladium (Pt-Pd), or the like is formed on the surface of the porous fiber by sputtering to prepare an observation sample. The cross section of the sample was observed with a scanning electron microscope (for example, S-5500 manufactured by Hitachi ハイテクノロジーズ Co., Ltd.). A transparent sheet is superimposed on an electron microscope image of an arbitrary fiber cross section printed by a scanning electron microscope (400 times), and the powder is blackened with a black pen or the like. In addition, a ruler and a black pen were also used to correctly delineate the scale. Thereafter, the transparent sheet was transferred to a piece of white paper, whereby the powder particles were black and the non-powder particles were white, and could be clearly distinguished. Then, the area occupancy (%) of the powder or granule can be determined by using image analysis software. As the Image analysis software, for example, "Analyze Particles" of "Image J" (openers wayne rasband (nih)) can be used to measure and determine the total area of the powder. The area ratio (%) of the powder/granular material is determined by the following equation 2. The electron microscopic image of the cross section of the porous fiber was taken of 30 arbitrary cross sections of the porous fiber, and the average value was calculated.
Area occupancy (%) of the powder of formula 2 = total area of powder/fiber cross-sectional area × 100%
It is also important that the porous fiber of the present invention does not contain the powder and granules having a diameter of 200 μm or less in a region within 1.0 μm in the depth direction from the outermost surface.
The term "in the depth direction from the outermost surface" as used herein means that the fiber has a meaning of being oriented from the surface of the porous fiber toward the depth direction at a perpendicular angle, i.e., toward the center of the porous fiber. Further, "a region within 1.0 μm" means the entire region having a depth of 1.0 μm and closer to the outer surface side than this. Therefore, the predetermined outer surface side "does not contain the powder or granule".
By reducing the amount of the particulate matter exposed on the outermost surface of the porous fiber, exposure of the particulate matter to the treatment liquid can be easily suppressed, and damage to the particulate matter due to stress of flow can be easily prevented. Such a configuration is particularly preferable in the case where blood is used as the liquid to be treated, because direct contact between the particulate matter and the blood cell component is suppressed, and activation of blood is easily reduced.
The "powder-free" in the present invention is defined as follows. That is, in the cross section of the porous fiber, the amount of the particulate matter contained in the region within 1.0 μm in the depth direction from the outermost surface is 3% or less of the total amount of the particulate matter contained in the cross section of the porous fiber. More preferably 2% or less, still more preferably 1% or less, and still more preferably 0.5% or less.
Here, when the fiber cross section is a shape other than a circle, 12 radii passing through the center point of the circle circumscribed by the fiber cross section are selected at 30 degree intervals, and points 1 μm from the outer surface below each radius are connected as regions within 1 μm from the outer surface. The ratio of the powder and granular material contained in the region within 1.0 μm in the depth direction from the outermost surface in the cross section of the porous fiber can be measured by the following method.
First, an observation sample was prepared in the same manner as in the area occupancy measurement, and the cross section of the sample was observed by a scanning electron microscope (e.g., S-5500 manufactured by Hitachi ハイテクノロジーズ Co., Ltd.). A transparent sheet is superimposed on an electron microscope image of an arbitrary fiber cross section printed by a scanning electron microscope (400 × magnification), and the powder is blackened with a black pen or the like. Thereafter, the transparent sheet was transferred to white paper, whereby the powder and granular material was clearly divided into black and non-powder portions and the area of the powder and granular material contained in the entire fiber cross section (a1) and the area occupied by the powder and granular material contained within 1 μm (a2) were obtained by image analysis software, and the areas were obtained as a2/a1 × 100%. The electron microscopic image of the cross section of the porous fiber was taken of 30 arbitrary cross sections of the porous fiber, and the average value was calculated.
Examples of the method for making the porous fiber not to contain the powder or granules having a diameter of 200 μm or less in the region within 1.0 μm in the depth direction from the outermost surface include a method of using a core liquid containing the powder or granules and a sheath liquid containing no powder or granules when spinning a porous fiber having a core-sheath structure described later.
In the present invention, examples of the particulate material that can be supported inside the fiber include carbon-based particulate materials such as charcoal, bamboo charcoal, activated carbon, carbon fiber, molecular sieve carbon, carbon nanotube, graphene, graphite, graphene oxide, mesoporous carbon, etc., silica gel, macroporous silica, activated alumina, zeolite, smectite, hydroxyapatite, metal hydroxide, inorganic particles such as metal carbonate, ion exchange resin, chelate resin, organic metal complex, organic particles such as chitosan, cellulose, etc., inorganic mesoporous material, organic-inorganic hybrid mesoporous material, carbon black gel, etc., and 1 or more of these materials can be used.
In the present invention, the powder or granule preferably selectively adsorbs low molecular compounds having a molecular weight of less than 1000. Here, the selective adsorption of low-molecular compounds having a molecular weight of less than 1000 means that low-molecular compounds having a molecular weight of less than 1000 are adsorbed more than high-molecular compounds having a molecular weight of 1000 or more in the blood concentration range of dialysis patients. The method for determining whether or not to selectively adsorb a low molecular compound having a molecular weight of less than 1000 is the same as the method for determining whether or not to selectively adsorb a high molecular compound having a molecular weight of 1000 or more, and when a sample is immersed in bovine plasma, the sample containing the powder or granules is regarded as a low molecular compound having a molecular weight of less than 1kDa if the adsorption performance of the sample on the average of 1g of the low molecular compound is higher than that of the sample containing no powder or granules. The method of obtaining the adsorption performance of 1g on average is also the same as the above-described method of determining whether or not a polymer compound having a molecular weight of 1000 or more is selectively adsorbed.
The low-molecular weight compound having a molecular weight of less than 1kDa is not particularly limited, and examples thereof include phosphoric acid, urea, uric acid, creatinine, indoxyl sulfate, homocysteine, and the like. Such low-molecular compounds are waste products deposited in the body of a dialysis patient, and are thus removal target substances for extracorporeal circulation.
For example, in the case where a low-molecular-weight compound such as phosphoric acid is used as the substance to be removed, the powder or granule in the porous fiber of the present invention is preferably an inorganic particle. In the porous fiber of the present invention, the particulate matter is preferably inorganic particles and has phosphorus adsorption performance. As the inorganic particles, preferred are a titanium oxide composite, a rare earth element hydroxide, a rare earth element-containing hydroxide, and a rare earth element carbonate. Here, the rare earth elements refer to 2 elements of scandium (Sc) having atomic number No. 21 and yttrium (Y) having atomic number 39 in the positions of the periodic table, and 17 elements in total of 15 elements of La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, lanthanum (La) to lutetium (Lu) having atomic number 57. Among them, carbonates of rare earth elements have low solubility in water and little change in pH in physiological saline, and therefore, they are particularly preferably used for medical applications.
Further, in the inorganic particles, it is most preferable that the rare earth element is selected from lanthanum, cerium, praseodymium, samarium and neodymium. In this case, the carbonate of the rare earth element is lanthanum carbonate, cerium carbonate, praseodymium carbonate, samarium carbonate, and neodymium carbonate. These carbonates of rare earth elements are particularly suitable for extracorporeal circulation because of low solubility in water, small pH change, and high adsorption performance of ionic low-molecular compounds.
Here, the extracorporeal circulation in the present invention refers to the return of blood from a living body to the body after inducing the blood to the outside of the body and removing a predetermined substance.
In addition, as another example, the molecular weight is reducedIn the case where the uremic toxin of the compound is a removal target substance, in the porous fiber of the present invention, the particulate matter preferably contains 1 or more selected from the group consisting of activated carbon, carbon nanotubes, graphene, graphite, and graphene oxide. The specific surface area of the powder is preferably 100 to 2500m 2 (ii)/g, more preferably 200 to 2000m 2 A/g, most preferably 300 to 1500m 2 (ii) in terms of/g. When the specific surface area is within the above range, the adsorption removal performance of the carbon-based powder particles is favorably exhibited. Further, uremic toxin refers to urea, uric acid, creatinine, indoxyl sulfate, homocysteine, and the like.
The powder or granule according to the present invention is preferably highly insoluble in water. That is, the solubility in water is preferably low. Here, the term "sparingly water-soluble" means that the solubility in 100g of water is 1mg or less, more preferably the solubility is 0.1mg or less, and most preferably the solubility is 0.01mg or less.
In the measurement of the solubility, 100g of water set to 20 ℃ in a thermostatic bath and a rotor were put into a flask, 1mg of the measured powder was put in, and stirred for 12 hours or more. Thereafter, filtration was performed using a filter paper of No.5A, and the insoluble component was weighed together with the filter paper dried at 60 degrees until reaching the weight. The difference between the charged amount of 1mg and the weight of the insoluble matter was defined as the solubility in 100g of water. When insoluble matter could not be filtered out, the solubility was recorded as more than 1 mg.
The porous fiber of the present invention preferably has a pH change of-1 or more and +1 or less.
Further, the porous fiber of the present invention more preferably has a pH change of-1.0 or more and +1.0 or less. More preferably from-0.8 to +0.8 (. + -. 0.8 or less), still more preferably within. + -. 0.6, and particularly preferably with the pH being substantially constant, i.e. + -. 0.1 or less.
In general, the pH balance in the environment and in the organism is very important, especially if the balance in the organism is disturbed, leading to a wide variety of diseases. The porous fiber of the present invention has little physiological change in pH of blood when it comes into contact with blood, and therefore has little influence on pH of body fluids such as blood. In the present invention, the change in pH in physiological saline is used as an index of whether the pH balance in vivo is excellent or not. Specifically, the change in pH was measured before and after the porous fiber was put into physiological saline and stirred at 200rpm for 4 hours.
As the pH measurement method, a glass electrode method, which is the most commonly used measurement method, is used. The method comprises the following steps: the pH of the target solution was measured by using 2 electrodes, i.e., a glass electrode and a reference electrode, and knowing the voltage (potential difference) generated between the 2 electrodes. Specifically, a compact pH meter LAQUATwin (コンパクト pH メータ LAQUATwin) manufactured by horiba, etc. can be used. In this apparatus, first, the calibration of the pH scale was carried out using known standard buffers (pH4.01 and 6.86). The pH of the physiological saline was measured and recorded as pH (initial). Thereafter, 0.1g of the measurement fiber was weighed, 10mL of the same physiological saline as described above was added, and the mixture was stirred at room temperature for 4 hours. 1mL of the sample was sampled, centrifuged at 9000rpm for 5 minutes, 500. mu.L of the supernatant was added to the measurement cell, and the pH was measured and recorded as pH (4H). The change in pH can be determined by equation 3.
Formula 3 pH change = pH (4H) -pH (start)
The porous fiber of the present invention preferably has a surface open area ratio in the range of 0.5% to 30.0%. The surface open area ratio of the porous fiber is preferably 0.5% or more, more preferably 1.5% or more, and particularly preferably 2.0% or more. It is preferable that the porosity be high because the substance to be removed in the treatment liquid is likely to diffuse to the adsorption sites inside the fibers. On the other hand, the upper limit is preferably 30%, more preferably 16%, and still more preferably 12%. If the open porosity is 30% or less, the fiber strength can be improved and the increase in surface roughness can be suppressed, which is preferable. Further, the fine particles generated inside the micropores are easily suppressed from flowing out of the fiber.
As a method for measuring the surface open area ratio, a cross section of a fiber obtained by the same method as that of the observation sample prepared in the above-described measurement of the area occupancy ratio of the particulate body was observed with a scanning electron microscope, and the cross section was observed at a magnification of 50000 (S-5500, manufactured by hitachi ハイテクノロジーズ co., ltd), and an image was read by a computer. The size of the read image may be 640 pixels × 480 pixels. The SEM image was cut out to a size of 6. mu. m.times.6 μm at an arbitrary position, and the image was analyzed by image processing software. By the binarization processing, a threshold value is determined so that the brightness is formed in the structural portion and the dark brightness is formed in the other portion, and an image in which the brightness portion is white and the dark brightness portion is black is obtained. In the case where the difference in contrast in the image is small and thus the structural part cannot be distinguished from other parts, the image is divided and binarized in the parts having the same range of contrast, and then the images are joined as they are and restored to one image. Alternatively, the image analysis may be performed by blacking out the portion other than the structural portion. Dark luminance portions in which the number of consecutive pixels is 5 or less, including noise, are treated as bright luminance portions as a structural body because noise and holes cannot be distinguished. As a method for eliminating noise, a dark luminance portion having a continuous number of pixels of 5 or less is excluded when the number of pixels is measured. Alternatively, the noise portion may be whitened. The number of pixels in the dark luminance portion was measured, and the percentage of the total number of pixels in the analysis image was calculated and recorded as the aperture ratio. The same measurement was performed on 30 images, and the average value was calculated.
The porous fiber in the present invention is in the form of a solid filament. In the case of a solid filament, the shape of the filament cross section is not necessarily limited to a true circle, and may be a deformed cross section. Examples of the irregular cross-sectional shape include an ellipse, a triangle, and a multilobal system. By providing the irregular cross section, the surface area per unit volume of the solid filament can be increased, and the adsorption performance is expected to be improved.
In addition, the porous fiber of the present invention is preferably a fiber having less risk of mechanical safety, spinnability, and separation of particles. Therefore, the porous fiber of the present invention is preferably a core-sheath type structure or an island-in-sea type structure. Further, if the encapsulated powder or granule is not peeled off and the porosity and micropores can be controlled, it can be achieved by a method in which the outer surface of the powder or granule encapsulating polymer is further coated with the same or different polymer.
In the case of the porous fiber having a core-sheath structure, either the homogeneous core type or the eccentric core type can be used, and the homogeneous core type is preferably used from the viewpoint of stability of the porous fiber and prevention of exposure of the powder and granular material.
In the porous fiber having a core-sheath structure, the thickness of the sheath portion is preferably 0.1 μm or more and 50 μm or less. If the thickness of the sheath is too thin, the spinnability is poor, and the particles may be eluted. On the other hand, if the thickness is too large, the removal target substance contained in the treatment target liquid may not diffuse into the fibers, and the adsorption performance of the powder or granule may not be sufficiently exhibited.
In the porous fiber having a core-sheath structure, the materials of the core portion and the sheath portion may have the same composition or different compositions, and preferably have viscosities close to each other. When the viscosity difference is close, peeling is less likely to occur at the core-sheath interface, which is preferable.
In the present invention, the sea-island structure refers to a multicore sea-island structure having a plurality of island components, and the powder or granule is preferably contained in the island components from the viewpoint of reducing exposure of the powder or granule. Further, by increasing the number of islands, the efficiency of adsorption of the powder or granule contained in the island component can be improved. The number of islands in the sea-island structure is preferably 2 to 300. Particularly, in consideration of the design of the spinning nozzle, spinning workability, fiber physical properties, processability and performance of the adsorbent, more preferably 5 to 50.
The porous fiber of the present invention is not limited to the core-sheath type porous fiber and the sea-island type porous fiber, and a porous fiber such as a common monofilament, a bimetal fiber, and a multilayer fiber can be used.
The porous fiber of the present invention preferably has a filament diameter of the solid fiber in a range of 20 μm to 1000 μm. The lower limit of the filament diameter of the solid fibers is preferably 20 μm, more preferably 50 μm, and still more preferably 100 μm. The upper limit is preferably 1000 μm, more preferably 800 μm, and still more preferably 500. mu.m. When the filament diameter of the solid fibers is 20 μm or more, the fiber strength is less likely to be reduced and productivity is likely to be improved even if the particle addition rate is increased. On the other hand, when the filament diameter of the fiber is 1000 μm or less, the filling rate of the porous fiber filled in the adsorption column tends to be increased, and the adsorption performance tends to be improved.
As a method for measuring the filament diameter of the fiber, 50 filaments (fibers) were arbitrarily extracted from among the filaments filled in the adsorption column. After the extracted filaments (fibers) were washed, the washing solution was completely replaced with pure water, and the filaments (fibers) were sandwiched between a glass slide and a cover glass. The outer diameter (outermost diameter) of the wire was measured at 2 arbitrary positions on the same wire using a projector (for example, V-10A manufactured by Nikon corporation), and the average value was taken, and the decimal point and the 1 st position were rounded. When the number of filaments to be filled is less than 50, all the filaments are measured and the average value is similarly obtained.
The material of the porous fiber in the present invention is not particularly limited, and organic materials are suitably used from the viewpoints of ease of molding processing, cost, and the like, and polymethyl methacrylate (hereinafter referred to as PMMA), polyacrylonitrile (hereinafter referred to as PAN), polysulfone, polyether sulfone, polyarylethersulfone, polypropylene, polystyrene, polycarbonate, cellulose triacetate, ethylene-vinyl alcohol copolymer, and the like can be used. Among them, materials containing an amorphous polymer and having a property of adsorbing proteins are preferable, and examples thereof include PMMA and PAN. PMMA and PAN are preferable because a structure having a sharp pore size distribution can be easily obtained. The porous fiber of the present invention is particularly preferably composed of polymethyl methacrylate (PMMA). Since PMMA is excellent in moldability and cost, and has high transparency, the internal state of the porous fiber is relatively easy to observe, and the state of contamination is easily evaluated. However, the inclusion of minor amounts of other ingredients is not excluded.
In addition, the porous fibers may be negatively charged. By including a negatively charged functional group in at least a part of the raw material, hydrophilicity increases, and micro-dispersion (i.e., formation of a large number of fine pores) tends to occur.
Examples of the material include materials having a substituent such as a sulfo group, a carboxyl group, an ester group, a sulfite group, a dithionite group, a sulfide group, a phenol group, or a hydroxysilyl group as a negatively charged functional group. Among them, at least 1 kind selected from a sulfo group, a carboxyl group, and an ester group is preferable.
Examples of the substance having a sulfo group include vinylsulfonic acid, acryloylsulfonic acid (アクリルスルホン acid), methacryloylsulfonic acid (メタクリルスルホン acid) p-styrenesulfonic acid, 3-methacryloyloxypropanesulfonic acid, 3-acryloyloxypropylpropanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, and sodium salts, potassium salts, ammonium salts, pyridine salts, quinoline salts, tetramethylammonium salts thereof.
The negative charge amount is preferably 5 μ eq or more and 30 μ eq or less per 1g of the dried fiber on average.
The amount of negative charge can be determined, for example, by titration.
In the following, an example of using a porous fiber having a core-sheath structure as a filament shape will be described with respect to an example of manufacturing the adsorption column according to the present invention, but the present invention is not limited thereto.
In particular, in the field of blood purification for medical use, it is known that various dialysis complications such as hyperphosphatemia due to insufficient removal of inorganic phosphorus and dialysis amyloidosis due to insufficient removal of β 2MG occur. Currently, oral phosphorus adsorbents are used for treating hyperphosphatemia, and β 2MG removal columns containing porous cellulose beads are used for dialysis amyloidosis. However, if both inorganic phosphorus and β 2MG can be adsorbed and removed simultaneously, QOL of patients is improved.
Therefore, in evaluating the adsorption performance of the porous fiber of the present invention, inorganic phosphorus is used as a low molecular weight compound of less than 1kDa as a removal target substance, a high molecular weight compound of 1kDa or more is used as a removal target substance, and the evaluation is performed with β 2MG as a removal target substance.
When the adsorptive performance per unit surface area of the adsorbing fiber is low, the adsorbing fiber is not preferable as an adsorbent, and even when packed in an adsorption column or the like, good adsorptive performance is not exhibited. The number of fibers to be packed has to be increased to ensure the adsorption performance, which leads to an increase in column volume, an increase in cost, and a decrease in handling property. In particular, in the case of using blood as the fluid to be treated, the amount of blood carried to the outside of the body increases, and thus, there is a possibility that a serious side effect such as a decrease in blood pressure is caused. Therefore, the fiber adsorption performance is excellent when the removal target substance is inorganic phosphorusIs selected to be 1.0mg/cm 3 More preferably 2.0mg/cm or more 3 More preferably 3.0mg/cm or more 3 Above, particularly preferably 4.0mg/cm 3 The above. In the present invention, the fact that the particulate matter has phosphorus adsorption performance means that the inorganic phosphorus adsorption performance of the fiber is 1.0mg/cm 3 As described above.
On the other hand, when the object to be removed is β 2MG, it is preferably 0.010MG/cm 2 Above, more preferably 0.015mg/cm 2 More preferably 0.020mg/cm 2 Above, particularly preferably 0.030mg/cm 2 As described above.
[ production of porous fiber ]
After dissolving a polymer serving as a raw material of the core portion in an appropriate solvent, a predetermined amount of selected powder is added to prepare a core liquid. The solvent differs depending on the kind of the polymer, and dimethylformamide, dimethylsulfoxide, hexanone, xylene, tetralin, cyclohexanone, carbon tetrachloride, etc. are generally used. For example, when PMMA is used as the polymer, dimethyl sulfoxide (DMSO) is preferably used.
The viscosity of the dope is important for making porous fibers. That is, if the viscosity is too low, the fluidity of the stock solution is high, and it is difficult to maintain the desired shape. Therefore, the lower limit of the stock solution viscosity is 10poise, more preferably 90poise, still more preferably 400poise, and particularly preferably 600 poise. On the other hand, if the viscosity is too high, the stability of discharge may be lowered due to an increase in pressure loss at the time of discharging the stock solution, and mixing of the stock solution may be difficult. Therefore, the upper limit of the dope viscosity at the temperature of the spinneret is 100000poise, more preferably 50000 poise.
The polymer serving as the raw material of the sheath liquid is preferably similar in viscosity to the dope of the core liquid, and more preferably has the same dope composition.
The spinning method for obtaining the fiber of the present invention may be either melt spinning or solution spinning, and in solution spinning, only the solvent is quickly removed from the state in which the support component is uniformly dissolved in the solvent, and thus a porous fiber having a relatively uniform structure is easily obtained, which is preferable. Therefore, the spinning dope preferably contains a matrix component such as a polymer and a solvent capable of dissolving the matrix component.
Hereinafter, a spinning method will be described by taking a porous fiber having a core-sheath structure spun from a solution as an example. The spinning dope is discharged from the spinneret and solidified into a solid filament shape by passing through a coagulation bath. When a porous fiber having a core-sheath structure is obtained as the spinneret, the spinneret may have a double-tube shape having annular slits, a triple-tube shape, or the like, and in particular, the double-tube shape is preferable to discharge the core liquid from the inside and the sheath liquid from the outside. The discharge amounts of the core liquid and the sheath liquid may be controlled by one gear pump, and more preferably, may be controlled by connecting the gear pumps to each other. The ratio of the amount of discharge of the core to the sheath can be easily changed by controlling the 2 gear pumps. For example, by making the ejection amount of the core constant and reducing the ejection amount of the sheath, a fiber with a thin sheath can be obtained.
In the case of a porous fiber having a sea-island structure, a conventional sea-island fiber spinneret can be used, and a design in which island portions are arranged uniformly is preferable as the spinneret shape. The coagulation bath usually contains a coagulant such as water or alcohol, or a mixture of a solvent and a coagulant constituting the spinning dope. In addition, by controlling the temperature of the coagulation bath, the porosity of the fiber can be changed. Since the porosity is affected by the type of the spinning dope, the temperature of the coagulation bath is also appropriately selected, and generally, the porosity can be increased by increasing the temperature of the coagulation bath. Although the mechanism thereof has not been correctly elucidated, it is considered that the solvent is rapidly removed in a high-temperature bath by a competitive reaction between the solvent removal from the stock solution and the solidification shrinkage, and the solid is solidified before the shrinkage. However, if the coagulation bath temperature is too high, the diameter of the micropores becomes too large, and therefore, for example, the coagulation bath temperature when solid filaments of PMMA are included as the base material and gas is introduced into the inner tube is preferably 20 ℃ or higher.
Then, the solvent adhering to the solidified solid filaments is washed. The means for washing the solid yarn is not particularly limited, and a method of passing the solid yarn in a multi-stage bath (water washing bath) provided with water is preferably used. The temperature of the water in the water bath is determined by the nature of the polymer constituting the filaments. For example, in the case of a filament comprising PMMA, 30 to 50 ℃ is used.
In addition, in order to maintain the diameter of the micropores in the solid filaments after passing through the water bath, a step of imparting a moisturizing ingredient may be added. The moisture-retaining component referred to herein is a component capable of retaining the humidity of the solid filaments or preventing the humidity of the solid filaments from being reduced in the air. As typical examples of the moisture-retaining component, glycerin, an aqueous solution thereof, and the like are given.
After the washing with water and the application of the moisture-retaining component, a step of filling a bath (heat treatment bath) with an aqueous solution of the heated moisture-retaining component may be performed in order to improve the dimensional stability of the solid yarn having high shrinkage. The heat treatment bath is filled with the heated aqueous solution of the moisture-retaining component, and the solid filaments pass through the heat treatment bath, whereby the solid filaments are shrunk by the action of heat, and are less likely to shrink in the subsequent step, and the filament structure can be stabilized. The heat treatment temperature at this time varies depending on the filament material, and in the case of a filament containing PMMA, it is preferably 75 ℃ or more, more preferably 82 ℃ or more. Further, the following is set: preferably 90 ℃ or lower, more preferably 86 ℃ or lower. The fiber spun in this manner is collected by winding it on a bobbin.
[ preparation of adsorption column ]
The adsorption column of the present invention is an adsorption column packed with the porous fiber of the present invention.
An example of a method for producing the adsorption column of the present invention using the porous fiber having a core-sheath structure produced as described above is shown below.
The shape of the outer shell of the adsorption column includes, for example, a prismatic tubular body such as a quadrangular tubular body or a hexagonal tubular body, and a cylindrical body, preferably a cylindrical body, particularly a cylindrical body having a true circular cross section. This is because the housing does not have corners, and thus the blood of the liquid to be treated can be prevented from staying at the corners. Further, by making both sides open, the flow of the liquid to be treated is less likely to become turbulent, and the pressure loss can be easily minimized.
Further, the housing is preferably an appliance made of plastic, metal, or the like. In the former case, the material can be manufactured by injection molding using a mold or by cutting the material. In the latter case, the tool can be produced by cutting the material. Among them, plastics are suitably used from the viewpoint of cost, moldability, weight, and blood compatibility.
In the case of plastic, for example, a thermoplastic resin having excellent mechanical strength and thermal stability can be used. Specific examples of such thermoplastic resins include polycarbonate resins, polyvinyl alcohol resins, cellulose resins, polyester resins, polyarylate resins, polyimide resins, cyclic polyolefin resins, polysulfone resins, polyether sulfone resins, polyolefin resins, polystyrene resins, polyvinyl alcohol resins, and mixtures thereof. Among these, polystyrene, polycarbonate, and derivatives thereof are preferable in terms of moldability, transparency, and radiation resistance required for the housing. The reason for this is that a resin having excellent transparency is advantageous in terms of ensuring safety because it allows the inside of the container to be confirmed during blood perfusion, and a resin having excellent radiation resistance is preferable when radiation is irradiated during sterilization.
The length of the outer shell of the adsorption column of the present invention is preferably 1cm to 500cm, more preferably 3cm to 50 cm. Here, the case length refers to the axial length of the cylindrical case before the partition wall is provided and the cover is attached. If the length of the outer shell of the adsorption column is 500cm or less, more preferably 50cm or less, the porous fiber is likely to be inserted into the adsorption column well, and it is considered that handling ease in practical use as an adsorption column is likely to be improved. Further, if the thickness is 1cm or more, more preferably 3cm or more, this is advantageous in the case of forming a partition wall, for example, and the handling property when the adsorption column is produced is improved.
The shape of the porous fiber when incorporated in the adsorption column is preferably a linear shape, and the linear fiber is preferably inserted in parallel to the longitudinal direction of the adsorption column housing. The linear porous fiber is advantageous in that it is easy to ensure a flow path for the liquid to be treated, and therefore, the liquid to be treated can be distributed uniformly in the adsorption column, and the flow path resistance can be easily suppressed, which is also advantageous in that the pressure loss due to adhesion of solute in the liquid to be treated can be increased. Therefore, in the case of using blood having high viscosity as the liquid to be treated, the risk of coagulation or the like in the casing can be easily suppressed to a small level. The porous fiber may also be processed into knitted fabric, woven fabric, nonwoven fabric, etc. However, since a large tension is applied to the yarn during processing, there is a limitation that the porosity of the porous fiber cannot be increased. Further, the processing of the porous fiber may increase the number of steps and the cost.
The number of the porous fibers contained in the adsorption column is preferably about 1000 to 500000.
The upper limit of the packing rate of the porous fibers in the outer shell of the adsorption column is preferably 70%, and more preferably 63%. The lower limit of the filling ratio of the porous fiber is preferably 13%, more preferably 30%, and particularly preferably 45%. By setting the filling ratio of the porous fiber to 13% or more, the amount of blood required for blood purification is reduced, and thus the burden on the patient can be easily reduced. Further, if the filling rate of the porous fiber is 70% or less, the air release property is easily improved. Further, since the porous fiber is easily filled, the work efficiency is easily improved. The filling factor referred to herein is a ratio of a volume of the porous fibers to a volume of a casing provided with an inlet into which a blood flow before purification flows and an outlet from which the blood flow after purification flows, and does not include a head portion and the like.
The filling factor is a ratio of a sheath volume (Vc) calculated from a cross-sectional area and a length of the sheath, a fiber cross-sectional area, a sheath length, and a fiber volume (Vf) calculated from the number of fibers, and is determined as follows.
Vc(cm 3 ) = cross-sectional area (cm) of case main body 2 ) X effective length (cm)
Vf(cm 3 ) = fiber cross-sectional area (cm) 2 ) X number of fibers x effective length (cm)
Fill ratio = Vf (cm) 3 )/Vc(cm 3 )×100(%)
In the case where the housing has a taper, the cross-sectional area of the housing at the center is taken as the cross-sectional area of the housing main body.
The volume of a member not containing porous fibers, for example, a member serving as an inlet/outlet port for the liquid to be treated, such as a head or a head cover, is not included in Vc. Further, Vf also includes a volume when spacer fibers or the like for preventing adhesion of porous fibers to each other in the casing are used. The effective length of the porous fiber is a length obtained by subtracting the length of the partition wall from the length of the outer shell, and the upper limit of the effective length of the porous fiber is preferably 5000mm, more preferably 500mm, and particularly preferably 210mm, from the viewpoints that the fiber is difficult to bend, and the pressure loss is easily reduced when the fiber is formed into a column. The lower limit of the effective length of the porous fiber is preferably 5mm, more preferably 20mm, and particularly preferably 30mm, from the viewpoints of reducing the amount of waste filaments when excess filaments protruding from the suction column are cut to make the lengths of the filaments uniform, facilitating improvement in productivity, facilitating handling of the fiber bundle, and the like. As a method for measuring the effective length of the fiber, in the case of applying a crimped yarn such as a crimp, the yarn length is measured in a state of a straight shape obtained by drawing both ends of the yarn. Specifically, one side of the fiber taken out from the adsorption column is fixed with an adhesive tape or the like, and vertically hung, and the other side is provided with a unit filament cross-sectional area (mm) 2 ) The total length of the fiber when it reached a straight line was measured quickly with a weight of about 8 g. This measurement is performed on 30 fibers arbitrarily selected in an adsorption column or the like, and an average value of 30 fibers is calculated in mm units, and the 1 st position after decimal point is rounded.
In addition, when used for medical instruments and the like, it is preferably used for sterilization or disinfection. Examples of the sterilization and sterilization method include various sterilization and sterilization methods, such as high-pressure steam sterilization, gamma ray sterilization, ethylene oxide gas sterilization, chemical sterilization, and ultraviolet sterilization. Among these methods, gamma ray sterilization, high-pressure steam sterilization, and ethylene oxide gas sterilization are preferable because they have little effect on the sterilization efficiency and materials.
The use of the adsorption column in the present invention is also various, and the adsorption column can be used for water treatment, purification, blood purification, and the like. In the case of the application to blood purification, there are a method of directly perfusing whole blood and a method of separating plasma from blood and then passing the plasma through an adsorption column, and the adsorption column of the present invention can be used in either method.
In addition, when used as a blood purifier, a method of performing adsorption and removal on line by being incorporated in an extracorporeal circuit is preferred from the viewpoints of 1-time throughput, simplicity of operation, and the like. In this case, the adsorption column of the present invention may be used alone, or may be used in series with an artificial kidney during dialysis or the like. By using such a method, it is possible to remove substances that are insufficiently removed by the artificial kidney alone while dialysis is performed. In particular, the adsorption column according to the present invention can be used to adsorb and remove inorganic phosphorus and β 2MG that are insufficiently removed by the artificial kidney, thereby supplementing the function of the artificial kidney.
In addition, when used together with an artificial kidney, the artificial kidney may be connected to the inside of the circuit before or after the artificial kidney. Since the advantage of being connected to the artificial kidney is that it is less susceptible to dialysis by the artificial kidney, the performance of the adsorption column itself is likely to be exhibited in some cases. On the other hand, as an advantage of being connected to the artificial kidney, blood or the like dehydrated by the artificial kidney is treated, and therefore the solute concentration is high, and an increase in the efficiency of the adsorption and removal of inorganic phosphorus can be expected.
The spinnability was evaluated as follows.
1: continuously spinning for 5hr without any filament breakage during spinning, and having excellent spinning property
2: when the spinning was carried out continuously for 5hr, the spinning properties were extremely poor, such as the number of yarn breaks during spinning being more than 3 or the nozzle pressure being 20kPa or more.
[ blood purification System ]
The blood purification system of the present invention is a blood purification system in which the adsorption column of the present invention and the dehydration column are connected.
As the blood purification system of the present invention, for example, the adsorption column and the dehydration column of the present invention may be connected in series to perform extracorporeal circulation. The dehydration column refers to a column for removing water from blood, and an artificial kidney may be used. At this time, blood flows through the side B as the inside of the hollow fiber in the same manner as dialysis, but the dialysate does not flow through the side D as the outside of the hollow fiber, and water is removed by filtration. By using such a method, water and waste other than water can be removed without using a dialysate, as in the case of artificial dialysis. Artificial dialysis removes waste by diffusion principle, but in the present invention, water is removed by filtration, and waste other than water is removed by adsorption.
Although the conventional artificial dialysis requires 100L or more of dialysate to be used at a time, the present method can expect the same effect as the artificial dialysis without using dialysate.
The upper limit of the blood volume of the artificial kidney for water removal is preferably 60mL, more preferably 50mL, and particularly preferably 40mL, while the lower limit thereof is preferably 10mL, more preferably 20mL, and particularly preferably 30 mL. If the blood volume is large, the amount of blood carried from the body at a time is large, and thus blood pressure may be lowered. On the other hand, if the blood volume is small, there is a possibility that the water removal effect cannot be sufficiently achieved.
The hollow fiber is contained in the dewatering column, but the material of the hollow fiber is not particularly limited, and polymethyl methacrylate, polyacrylonitrile, polysulfone, polyether sulfone, polyarylethersulfone, polypropylene, polystyrene, polycarbonate, cellulose triacetate, ethylene-vinyl alcohol copolymer, and the like which have been used in clinical practice can be used.
Examples
The present invention will be described below with reference to examples.
In examples, various particles were used as the powder. In addition, inorganic phosphorus was selected as a model substance of a low molecular compound and β 2MG was selected as a model substance of a high molecular compound for a removal target substance. However, the present invention is not limited to these examples.
[ examples 1to 2]
< preparation of dope for dope spinning >
First, a 21 mass% PMMA stock solution was prepared. 31.7 parts by mass of syndiotactic-PMMA having a mass-average molecular weight of 40 ten thousand (syn-PMMA, manufactured by Mitsubishi レイヨン, "ダイヤナール" BR-85), 31.7 parts by mass of syn-PMMA having a mass-average molecular weight of 140 ten thousand (manufactured by Sumitomo chemical Co., Ltd., "スミペックス" AK-150), 16.7 parts by mass of isotactic-PMMA having a mass-average molecular weight of 50 ten thousand (iso-PMMA, manufactured by east レ), 20 parts by mass of a PMMA copolymer having a molecular weight of 30 ten thousand and containing 1.5mol% of sodium p-styrenesulfonate (manufactured by east レ Co., Ltd.) and 376 parts by mass of dimethyl sulfoxide (DMSO) were mixed and stirred at 110 ℃ for 8 hours to prepare a dope.
In example 1, 190g of dimethyl sulfoxide and 100g of titanium oxide particles as a particulate material to be a phosphorus adsorbent were added to the spinning solution 476g obtained above to prepare a titanium oxide/PMMA solution containing 50 mass% of the particulate material, and the solution was stirred at 110 ℃ for 5 hours to prepare a core solution. The resulting stock had a viscosity of 750 poise.
On the other hand, in example 2, 50g of neodymium carbonate as a phosphorus adsorbent was added to the dope 476g obtained as described above as a powder, to prepare a neodymium carbonate/PMMA dope containing 50 mass% of the powder fluid, and the dope was stirred at 110 ℃ for 5 hours to prepare a dope. The resulting stock solution had a viscosity of 1200 poise.
< preparation of sheath fluid spinning dope >
32.4 parts by mass of syn-PMMA having a mass average molecular weight of 40 ten thousand, 32.4 parts by mass of syn-PMMA having a mass average molecular weight of 140 ten thousand, 16.7 parts by mass of iso-PMMA having a mass average molecular weight of 50 ten thousand and 355 parts by mass of dimethyl sulfoxide were mixed, and stirred at 110 ℃ for 8 hours to prepare a spinning dope. The resulting stock had a viscosity of 2650 poise.
< spinning >)
An annular slit-type spinneret having an outer diameter/inner diameter =2.1/1.95mm phi was used. The temperature of the spinneret was raised to 100 ℃ to discharge the sheath liquid at a rate of 0.673g/min from the slit portion and the core liquid at a rate of 0.735g/min from the center portion. The sprayed stock solution was advanced 500mm in the air and then introduced into a coagulation bath. Water was used in the coagulation bath, and the water temperature (coagulation bath temperature) was 42 ℃. The silk was washed in a water bath, introduced into a bath containing an aqueous solution containing 70 mass% glycerin as a humectant, and then passed through a heat treatment bath at 84 ℃ to be wound on a bobbin at 16 m/min.
After washing the obtained porous fiber having a core-sheath structure, the washing solution was completely replaced with pure water, and the fiber was sandwiched between a glass slide and a cover glass, and the outer diameter (outermost diameter) of the same fiber was measured at 2 arbitrary positions on the same fiber using a projector (for example, V-10A manufactured by Nikon corporation), and the average value was taken, and the 1 st position after the decimal point was rounded off and recorded as the fiber diameter.
Comparative example 1
Spinning was carried out using the same dope composition and spinneret as in example 1. At this time, the amount of the sheath ejected from the slit portion of the spinneret was set to 0 g/min.
Comparative example 2
Spinning was carried out using the same dope composition and spinneret as in example 2. At this time, the amount of the sheath ejected from the slit portion of the spinneret was set to 0 g/min.
Comparative example 3
Nylon, which is a non-porous fiber, is used instead of the porous fiber.
The evaluation results of the adsorption performance of inorganic phosphorus and β 2MG of the porous fibers and the non-porous fibers of examples 1to 2 and comparative examples 1to 3 are shown in tables 1 and 2.
< measurement method >
(1) Method for preparing liquid to be treated
The liquid to be treated was used by treating bovine blood as described below.
First, 15mL of citric acid (ACD-A solution, テルモ) was added to 100mL of bovine blood, and the obtained bovine blood was centrifuged at 3000rpm for 30 minutes to obtain bovine plasma. Adjusted to achieve a total protein amount (TP) of 6.5 + -0.5 g/dL for the bovine plasma. As bovine plasma, plasma obtained within 5 days after blood collection was used.
Next, 7.85mg of disodium hydrogenphosphate (Na) was added to the bovine plasma so that the concentration of inorganic phosphorus in the bovine plasma was 6mg/dL per 100mL of the mixture 2 HPO 4 ) And 3.45mg of monopotassium phosphate (KH) 2 PO 4 )。
Further, β 2MG was added so that the concentration of β 2MG became 1MG/L relative to 100mL of the bovine plasma, thereby preparing a treatment target solution.
The inorganic phosphorus concentration of the treatment liquid was measured by the following method. That is, 200. mu.L of the liquid to be treated was stored in a freezer at a temperature of-20 ℃ or lower, and then sent to a slide fire laboratory (slide Long ライフサイエンスラボラトリー) of オリエンタル Yeast Industrial Co., Ltd. to measure the inorganic phosphorus concentration by an enzymatic method using Determinar L IPII, and the concentration was designated as C1 (mg/dL).
On the other hand, the β 2MG concentration in the treatment target liquid was measured by the following method. That is, 1mL of the liquid to be treated was stored in a freezer at a temperature of-20 ℃ or lower, and then sent to エスアールエル, where the concentration of β 2MG was measured by latex agglutination and recorded as C2 (MG/mL).
(2) Adsorption Property
The porous fibers obtained in examples 1to 2 and comparative examples 1to 2 and the nylon of comparative example 3 were cut into bundles having a length of 8cm such that the volume of the fibers reached 0.0905cm 3 The resulting mixture was put into a 15mL centrifugal tube manufactured by グライナー. To this was added 12mL of the liquid to be treated, and the mixture was stirred at room temperature (20 to 25 ℃) for 1 hour with a scale of 38 and a maximum angle (1.7 seconds and 1 round trip) set by using Wave-SI manufactured by TAITEC corporation in this example, using a shaker (seeslow shaker). In order to measure the inorganic phosphorus concentration C3(MG/dL) and the β 2MG concentration C4(MG/mL) after the stirring, 1.5mL of each sample was sampled, centrifuged at 9000rpm for 5 minutes, and the supernatant was collected. The samples before and after stirring were stored in a freezer at-20 ℃ or below. The inorganic phosphorus concentration was measured in the supernatant, which was sent to オリエンタル Changchama life science laboratory (Changchama ライフサイエンスラボラトリー). The β 2MG concentration was sent to エスアールエル, and the amount of adsorbed inorganic phosphorus per fiber volume was calculated from formula 4 and the amount of adsorbed β 2MG per fiber surface area was calculated from formula 5, by measurement using a latex agglutination method.
Adsorption per fiber volume of formula 4Amount [ mg/g ] = [ (C1-C3). times.0.12 (dL) ] per total volume of porous fiber (cm) 3 )
Adsorption amount per unit fiber surface area (μ g/cm) of formula 5 2 ) = (C2-C4) × 12 per total surface area of fiber (cm) 2 ) X 1000 porous fiber
(3) Powder dissolution amount measurement
The porous fibers obtained in examples 1to 2 and comparative examples 1to 2 and the nylon of comparative example 3 were cut into pieces having a length of 10cm, 250 pieces were put into a 50mL centrifuge tube manufactured by グライナー, and first, 40mL of an Otsuka injection water was used for washing 5 times, and the 5 th washing solution was sampled and described before stirring (N1). Thereafter, 40mL of water for injection was further added, and the mixture was stirred at room temperature (20 to 25 ℃) for 1 hour with a maximum angle (1.7 seconds and 1 round trip) set at 38 degrees by using a shaking shaker or the like, for example, Wave-SI manufactured by TAITEC corporation, and the resulting solution was referred to as a stirred eluate (N2). The washing solution and the eluted solution were measured by a particle counter (KL-04, manufactured by RION), and the number of particles eluted was calculated from equation 6.
Formula 6 the number of dissolved microparticles = N2-N1
(4) Wire diameter measurement
The test piece was sandwiched between a slide glass and a cover glass, and measured by using V-10 manufactured by Nikon.
(5) Average pore diameter
Measured by Differential Scanning Calorimetry (DSC).
(6) Area occupancy of powder
Measured and calculated by an electron microscope (SEM) (S-5500, manufactured by Hitachi ハイテクノロジーズ Co., Ltd.) by the method described above.
[ example 3]
< preparation of adsorption column >
A plurality of the porous fibers obtained in example 1 were each filled in a cylindrical casing made of polycarbonate having an inner diameter of 10mm and an axial length of 17.8 mm.
More specifically, the filament having a filament diameter of 290 μm obtained in example 1 was cut into a length of 17.8mm, and 655 pieces were packed in total, to obtain a column having a packing ratio of 55.1%. Subsequently, a polypropylene mesh filter cut to have a mesh equivalent diameter of 84 μm equal to the inner diameter of the housing and an aperture ratio of 36% was attached to the inlet and outlet of the liquid to be treated on both side end faces of the column. Finally, a cap called a head having an inlet and an outlet for the liquid to be treated was attached to the end of the housing to obtain an adsorption column. The obtained adsorption column was evaluated based on the following determination of phosphorus adsorption performance of the adsorption column. The results are shown in Table 3.
[ example 4]
The yarn having a yarn diameter of 170 μm obtained in example 2 was cut into a length of 17.8mm, and 760 pieces of the yarn were packed in the same adsorption column as in example 3 in total to obtain an adsorption column having a packing rate of 22.2%. The obtained adsorption column was evaluated based on the following "measurement of phosphorus adsorption performance of adsorption column". The results are shown in Table 3.
< determination of phosphorus adsorption Property of adsorption column >
As evaluation of adsorption performance, phosphorus adsorption performance of the adsorption column was measured. Bovine plasma was obtained in the same manner as in the evaluation of the adsorption performance of examples 1to 2 and comparative examples 1to 3. Adjusted to achieve a total protein amount of 6.5 ± 0.5g/dL for the bovine plasma. The bovine plasma was used within 5 days after the blood collection. Next, 7.85mg of disodium hydrogenphosphate (Na) was dissolved in an average volume of 100mL of the bovine plasma 2 HPO 4 ) And 3.45mg of monopotassium phosphate (KH) 2 PO 4 ) A treatment solution simulating hyperphosphatemia was prepared.
Silicone tubes were attached to the inlet and outlet of the adsorption column, and both the inlet and outlet were immersed in the treatment target liquid to prepare a circulation system. The liquid to be treated flowed at a flow rate of 2.5mL/min, and after passing through the adsorption column from the inlet of the adsorption column, the purified liquid was returned to the liquid to be treated from the outlet. The treated liquid and the purified liquid at the outlet were sampled to determine the inorganic phosphorus concentration in the sample.
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Figure 421581DEST_PATH_IMAGE002
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Claims (15)

1. A porous fiber having a three-dimensional microporous structure formed by a solid-shaped fiber, the solid-shaped fiber having a filament diameter in a range of 20 μm or more and 1000 μm or less, and satisfying all of the following requirements:
(1) a powder or granule having a diameter of 200 [ mu ] m or less, wherein the powder or granule having a diameter of 200 [ mu ] m or less has an area occupancy of 3.0% or more in a cross section of the three-dimensional microporous structure;
(2) the powder and granular material having a diameter of 200 μm or less is not contained in a region within 1.0 μm in the depth direction from the outermost surface.
2. The porous fiber according to claim 1, wherein the average pore radius of the three-dimensional pore structure is in a range of 0.5nm or more and 100nm or less.
3. The porous fiber according to claim 1 or 2, wherein the surface open porosity is in the range of 0.5% or more and 30.0% or less.
4. The porous fiber according to claim 1 or 2, wherein the specific surface area of the micropores in the three-dimensional microporous structure is 10m 2 More than g.
5. The porous fiber of claim 1 or 2, which is a core-sheath type structure or an island-in-sea type structure.
6. The porous fiber according to claim 1 or 2, wherein the powder is an inorganic particle.
7. The porous fiber according to claim 1 or 2, wherein the powder contains 1 or more selected from the group consisting of activated carbon, carbon nanotubes, graphene, graphite, and graphene oxide.
8. The porous fiber according to claim 1 or 2, wherein the powder selectively adsorbs a low molecular compound having a molecular weight of less than 1000.
9. The porous fiber according to claim 1 or 2, wherein the particulate is an inorganic particle and has a phosphorus adsorption property.
10. The porous fiber according to claim 1 or 2, wherein micropores in the three-dimensional microporous structure selectively adsorb a high molecular compound having a molecular weight of 1000 or more.
11. The porous fiber according to claim 1 or 2, which is composed of polymethyl methacrylate.
12. The porous fiber according to claim 1 or 2, wherein the pH change is-1 to +1, using horiba, the compact pH meter LAQUAtwin, the instrument, first, using known standard buffer solution, pH4.01 and 6.86, respectively, pH calibration, measurement of physiological saline pH, recorded as pH (start), thereafter, weighing the fiber for measurement of 0.1g, adding the same physiological saline 10mL, at room temperature for 4 hours stirring, sampling 1mL, in 9000rpm centrifugal separation for 5 minutes, supernatant 500L to the measuring chamber, measured pH, recorded as pH (4H), pH change through the equation 3 to determine,
formula 3 pH change = pH (4H) -pH (start).
13. The porous fiber of claim 1 or 2, for medical use.
14. An adsorption column packed with the porous fiber according to any one of claims 1to 13.
15. A blood purification system comprising the adsorption column according to claim 14 and a water removal column connected to each other.
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